CN105921172A - Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method - Google Patents
Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method Download PDFInfo
- Publication number
- CN105921172A CN105921172A CN201610340067.9A CN201610340067A CN105921172A CN 105921172 A CN105921172 A CN 105921172A CN 201610340067 A CN201610340067 A CN 201610340067A CN 105921172 A CN105921172 A CN 105921172A
- Authority
- CN
- China
- Prior art keywords
- propylene glycol
- ionic liquid
- expoxy propane
- glycol ether
- emim
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/48—Ring-opening reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical catalysis and provides application of ionic liquid in synthesis of propylene glycol ether and a propylene glycol ether synthesis method. The ionic liquid is imidazole acetate ionic liquid and/or quaternary amine acetate ionic liquid, serves as a catalyst for catalyzing synthesis of the propylene glycol ether. The propylene glycol ether synthesis method includes the following steps that epoxy propane and alcohol are added to a reactor to be in contact with the catalyst, heating is performed in a closed environment to reach 50-200 DEG C, the propylene glycol ether is obtained, wherein the catalyst is the acetate ionic liquid and/or the quaternary amine acetate ionic liquid. The propylene glycol ether synthesis method is a green synthesis process, has not special production equipment requirements and facilitates industrial production and application, and the process is simple and easy to control.
Description
Technical field
The invention belongs to chemical catalysis field, be specifically related to ionic liquid application in propylene glycol synthesizes and propylene glycol synthetic method.
Background technology
Propylene glycol is that the reaction of one of essential industry derivative of epoxide, predominantly expoxy propane and alcohols prepares, owing to propylene glycol has
The group-ol ether of two strong dissolving functions and hydroxyl so that it has the strongest solubility property.Be referred to as alembroth, be widely used in coating,
Ink, paint, printing etc..Steric effect due to expoxy propane so that the position of expoxy propane open loop under conditions of bronsted lowry acids and bases bronsted lowry can be different, then
With alcohols generation addition reaction, alkali generates 1-methoxy-2-propanol, and acid generates 2-methoxy-1-propanol.The catalyst of this reaction have acid, alkali,
Some salt and oxide, mainly soda acid homogeneous catalyst.Catalyst conventional in domestic industry is NaOH, BF3, sodium alkoxide, potassium alcoholate, but this
A little catalyst all also exist etching apparatus, it is difficult to the shortcomings such as recycling.
Summary of the invention
The technical problem to be solved is to overcome the defect of prior art, it is provided that ionic liquid application and the third two in propylene glycol synthesizes
Alcohol ether synthetic method.
The present invention provides the application in propylene glycol synthesizes of a kind of ionic liquid, and described ionic liquid is imidazoles acetate ionic liquid and/or quaternary amine
Class acetate ionic liquid, it is as catalyst synthesis of propylene glycol.
Present invention also offers a kind of propylene glycol synthetic method, described method comprises the steps:
Expoxy propane is sent in reactor with alcohol and contacts with catalyst, be heated to 50 DEG C～200 DEG C under closed environment, it is thus achieved that described propylene glycol,
Wherein, described catalyst is acetate ionic liquid and/or quaternary ammonium acetate ionic liquid.
The present invention provides the application in propylene glycol synthesizes of a kind of ionic liquid, and described ionic liquid is imidazoles acetate ionic liquid and/or quaternary amine
Class acetate ionic liquid.Such ionic liquid is halogen-free green ionic liquid, and not etching apparatus has good base catalysis effect.Alcohols
Compound is deprotonated in the effect of imidazoles acetate ionic liquid and/or quaternary ammonium acetate ionic liquid, generates alkoxy radical ionic liquid, then
Carry out addition with expoxy propane and generate monoether.Further, such catalyst preparation process is simple, and production cost is low, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention bromthymol blue (BTB) and adds NaOH, [N2221] [AC], purple after [DMIM] [AC] and triethylamine
Outer absorption is schemed.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is carried out further
Describe in detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provide a kind of ionic liquid propylene glycol synthesize in application, described ionic liquid be imidazoles acetate ionic liquid and
/ or quaternary ammonium acetate ionic liquid, it is as catalyst synthesis of propylene glycol.
Specifically, described alcohol is C1～C8Any one in alcohol, such as methyl alcohol, ethanol, propyl alcohol, butanol, the tert-butyl alcohol, amylalcohol, hexanol,
The alkyl such as enanthol, the octanol alcohol less than or equal to 8.Described imidazoles acetate ionic liquid is [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC]
In at least one, described quaternary ammonium acetate ionic liquid is [N2221][AC]、[N4441] [AC] and [N4444] at least one in [AC].Its structure
Formula is as follows:
Further, it is preferable that described ionic liquid is at least one in [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC].Imidazoles
Ionic liquid has higher heat endurance relative to other ionic liquids such as quaternary ammonium ionic liquid, tetramethyl guanidine ionic liquid etc., in catalysis fourth
The alkyl such as alcohol, the tert-butyl alcohol, amylalcohol, hexanol, enanthol, the octanol alcohol more than or equal to 4 reacts with expoxy propane and has bigger advantage.Also
That is on the significant cyclic number of catalyst, imidazoles acetate ionic liquid has bigger advantage.Therefore, either from the prices of raw materials
On, or in utilization ratio, imidazoles acetate ionic liquid has bigger industrial application value.It is highly preferred that described ionic liquid is
[EMIM][AC]。
Hammett-ultraviolet method bromthymol blue is utilized to detect NaOH, [N as indicator2221] [AC], [DMIM] [AC] and the base strength of triethylamine.
At 433nm, the absworption peak of a hydroxyl is had, along with the absworption peak at 433nm that is added in of hydroxide ion disappears and occurs in the case of alkali-free
Red shift produces a new absworption peak at 620nm, as Fig. 1 bromthymol blue (BTB) and BTB add NaOH, [N2221][AC]、
Shown in UV absorption figure after [DMIM] [AC] and triethylamine, wherein, the concentration of bromthymol blue is 1.6 × 10-6mol/L.Absorption at 620nm
Peak is that along with being continuously increased of hydroxide ion concentration, its intensity is continuously increased, and works as increase owing to the hydrogen on phenolic group on molecule occurs transfer to be caused
Do not increasing time to a certain extent.Bromthymol blue indicator and substantial amounts of hydroxide ion effect, by making the hydrogen on identification point leave away, which increase
The cloud density of the oxygen atom on phenolic hydroxyl group, again due to the conjugation of π key big on phenyl ring thus cause intramolecular electric charge to shift, result in 620
The generation at the new peak of nm, solution becomes blue simultaneously.
In the environment of identical, the order of base strength is NaOH ＞ triethylamine ＞ [DMIM] [AC] ＞ [N2221] [AC], this explains imidazoles acetic acid
Ionic liquid and/or quaternary ammonium acetate ionic liquid activity aspect are not as NaOH, but are selectively more than NaOH at identical conditions,
30% can be exceeded under certain condition, and pollution-free, little to equipment corrosion.
Present invention also offers a kind of propylene glycol synthetic method, described method comprises the steps:
Expoxy propane is sent in reactor with alcohol and contacts with catalyst, be heated to 50 DEG C～200 DEG C under closed environment, it is thus achieved that described propylene glycol,
Wherein, described catalyst is imidazoles acetate ionic liquid and/or quaternary ammonium acetate ionic liquid.
Specifically, described expoxy propane is 1:1～1:10 with the mol ratio of alcohol, and described catalyst is 1:10～1 with the mol ratio of expoxy propane:
1000, the reaction time 30～300min.Pressure is usually between 0.1～1MPa.Preferably, the mol ratio of described expoxy propane and alcohol be 1:5～
1:4, described catalyst is 1:50～1:200 with the mol ratio of expoxy propane.It is highly preferred that described alcohol is C1～C8Any one in alcohol.
Described imidazoles acetate ionic liquid is at least one in [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC], described quaternary ammonium
Acetate ionic liquid is [N2221][AC]、[N4441] [AC] and [N4444] at least one in [AC].Further, it is preferable that described ionic liquid is
At least one in [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC].It is highly preferred that described ionic liquid is [EMIM] [AC].
Ionic liquid application in propylene glycol synthesizes and the synthetic method of propylene glycol is illustrated below by way of specific embodiment.Implement below
Ionic liquid in example can directly be prepared according to existing method respectively, certainly, can also buy the most from the market in other embodiments, and
It is not limited to this.
Embodiment 1:
The synthesis of ionic liquid [N2221] [AC]:
1.91g [N2221] [MC], 1.2g acetic acid in 3mL water, 1h is stirred at room temperature after reaction generate, in course of reaction, methyl carbonic acid root from
Sub-liquid [N2221] [MC] generates water and carbon dioxide with acetic acidreaction, ultimately generates [N2221] [AC], by obtained solvent ether washing 3
After secondary, it be vacuum dried at 50 DEG C, obtain the crystallization of yellow.
It is the expoxy propane of 1:3:0.01, methyl alcohol and [N by mol ratio2221] [AC] send in microwave reaction pipe, at microwave reactor after mixing
In, it is heated to 50 DEG C, reacts 30min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio of expoxy propane is 2.5%, and the selectivity of propylene glycol monomethyl ether is 89.6%.
Embodiment 2:
The synthesis of ionic liquid [EMIM] [AC]:
Potassium acetate (1.0mol) is dissolved at 70 DEG C 700mL absolute methanol, and 1-ethyl-3-methyllimidazolium bromide bromide [EMIM] [Br]
(1.0mol) it is dissolved in 100mL absolute methanol, subsequently liquor kalii acetici is added drop-wise to 1-ethyl-3-methyllimidazolium bromide Acetate Solution in 5 minutes
In, constantly there is KBr solid to separate out during dropping, after being added dropwise to complete, react 2h, whole process reaction temperature is 70 DEG C.By the most molten for reaction
Liquid cooled and filtered removes KBr, and filtrate removes absolute methanol by the way of decompression is distilled, and finally obtains pale yellow transparent and glues the liquid 1-ethyl of shape
-3-methylimidazole acetate [EMIM] [Ac].
It is to send in microwave reaction pipe, at microwave reaction after the expoxy propane of 1:3:0.01, methyl alcohol and [EMIM] [AC] mix by mol ratio
In device, it is heated to 200 DEG C, reacts 300min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio drawing expoxy propane is 99.8%, and the selectivity of propylene glycol monomethyl ether is 81.4%.
Embodiment 3:
It is to send in reactor after the expoxy propane of 1:1:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 30min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 94.55%, the selectivity of propylene glycol monobutyl ether is 64.66%.
Embodiment 4:
It is to send in reactor after the expoxy propane of 1:1:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 60min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 96.19%, the selectivity of propylene glycol monobutyl ether is 63.8%.
Embodiment 5:
It is to send in reactor after the expoxy propane of 1:1:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 120min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 95.05%, and the selectivity of propylene glycol monobutyl ether is 64.85%.
Embodiment 6:
It is to send in reactor after the expoxy propane of 1:1:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 180min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 95.56%, and the selectivity of propylene glycol monobutyl ether is 64.56%.
Embodiment 7:
It is to send in reactor after the expoxy propane of 1:1:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 240min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 96.54%, and the selectivity of propylene glycol monobutyl ether is 63.73%.
Embodiment 8:
It is to send in reactor after the expoxy propane of 1:3:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 30min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 92.73%, the selectivity of propylene glycol monobutyl ether is 86.84%.
Embodiment 9:
It is to send in reactor after the expoxy propane of 1:3:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 60min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 95.81%, the selectivity of propylene glycol monobutyl ether is 86.8%.
Embodiment 10:
It is to send in reactor after the expoxy propane of 1:3:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 120min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 97.59%, and the selectivity of propylene glycol monobutyl ether is 86.37%.
Embodiment 11:
It is to send in reactor after the expoxy propane of 1:3:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 180min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 97.9%, and the selectivity of propylene glycol monobutyl ether is 86.45%.
Embodiment 12:
It is to send in reactor after the expoxy propane of 1:3:0.01, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 240min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 98.12%, and the selectivity of propylene glycol monobutyl ether is 86.26%.
Embodiment 13:
It is to send in reactor after the expoxy propane of 1:3:0.001, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 120min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 57.03%, and the selectivity of propylene glycol monobutyl ether is 95.05%.
Embodiment 14:
It is to send in reactor after the expoxy propane of 1:3:0.001, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 180min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 66.37%, and the selectivity of propylene glycol monobutyl ether is 95.11%.
Embodiment 15:
It is to send in reactor after the expoxy propane of 1:3:0.001, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 240min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 70.88%, and the selectivity of propylene glycol monobutyl ether is 96.18%.
Embodiment 16:
It is to send in reactor after the expoxy propane of 1:3:0.003, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 60min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 75.92%, the selectivity of propylene glycol monobutyl ether is 95.05%.
Embodiment 17:
It is to send in reactor after the expoxy propane of 1:3:0.003, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 120min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 91.22%, and the selectivity of propylene glycol monobutyl ether is 85.15%.
Embodiment 18:
It is to send in reactor after the expoxy propane of 1:3:0.003, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 180min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 93.77%, and the selectivity of propylene glycol monobutyl ether is 84.91%.
Embodiment 19:
It is to send in reactor after the expoxy propane of 1:3:0.003, butanol and [EMIM] [AC] mix by mol ratio, is heated to 120 DEG C,
Reaction 240min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion of expoxy propane
Rate is 94.66%, and the selectivity of propylene glycol monobutyl ether is 84.38%.
Embodiment 20:
It is to send in microwave reaction pipe, at microwave reaction after the expoxy propane of 1:3:0.005, butanol and [EMIM] [AC] mix by mol ratio
In device, it is heated to 120 DEG C, reacts 30min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio drawing expoxy propane is 77.41%, and the selectivity of propylene glycol monobutyl ether is 87.94%.
Embodiment 21:
It is to send in microwave reaction pipe, at microwave reaction after the expoxy propane of 1:3:0.005, butanol and [EMIM] [AC] mix by mol ratio
In device, it is heated to 120 DEG C, reacts 60min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio drawing expoxy propane is 91.67%, and the selectivity of propylene glycol monobutyl ether is 86.5%.
Embodiment 22:
It is to send in microwave reaction pipe, at microwave reaction after the expoxy propane of 1:3:0.005, butanol and [EMIM] [AC] mix by mol ratio
In device, it is heated to 120 DEG C, reacts 120min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio drawing expoxy propane is 96.9%, and the selectivity of propylene glycol monobutyl ether is 85.71%.
Embodiment 23:
It is to send in microwave reaction pipe, at microwave reaction after the expoxy propane of 1:3:0.005, butanol and [EMIM] [AC] mix by mol ratio
In device, it is heated to 120 DEG C, reacts 180min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio drawing expoxy propane is 97.34%, and the selectivity of propylene glycol monobutyl ether is 85.8%.
Embodiment 24:
It is the expoxy propane of 1:1:0.001, octanol and [N by mol ratio4441] [AC] send in reactor after mixing, and is heated to 80 DEG C, instead
Answer 300min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 97.7%, the selectivity of propane diols list octyl ether is 90.5%.
Embodiment 25:
It is to send in reactor after the expoxy propane of 1:1:0.1, octanol and [BMIM] [AC] mix by mol ratio, is heated to 200 DEG C, instead
Answer 300min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 85.6%, the selectivity of propane diols list octyl ether is 91.5%.
Embodiment 26:
It is to send in reactor after the expoxy propane of 1:1:0.1, ethanol and [DMIM] [AC] mix by mol ratio, is heated to 200 DEG C, instead
Answer 300min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates the conversion ratio of expoxy propane
Being 99.9%, the selectivity of dihydroxypropane single-ether is 74.3%.
Embodiment 26:
It is to send into reactor after the expoxy propane of 1:1:0.05:0.05, hexanol, [BMIM] [AC] and [DMIM] [AC] mix by mol ratio
In, it is heated to 200 DEG C, reacts 300min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio going out expoxy propane is 77.9%, and the selectivity of propane diols monohexyl ether is 82.4%.
Embodiment 27:
It is to send into reactor after the expoxy propane of 1:1:0.03:0.07, hexanol, [BMIM] [AC] and [DMIM] [AC] mix by mol ratio
In, it is heated to 200 DEG C, reacts 300min.The mixture obtained is utilized the composition of the liquid phase mixture that gas chromatography determination obtains, calculates
The conversion ratio going out expoxy propane is 81.7%, and the selectivity of propane diols monohexyl ether is 81.8%.
Embodiment 28:
It is the expoxy propane of 1:1:0.03:0.03:0.04, hexanol, [BMIM] [AC], [N by mol ratio4441] [AC] and [DMIM] [AC] mix
Send in reactor after closing uniformly, be heated to 100 DEG C, react 200min.The liquid phase that the mixture obtained utilizes gas chromatography determination to obtain is mixed
The composition of compound, the conversion ratio calculating expoxy propane is 84.2%, and the selectivity of propane diols monohexyl ether is 85.7%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all made within the spirit and principles in the present invention
Any amendment, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the ionic liquid application in propylene glycol synthesizes, it is characterised in that described ionic liquid be imidazoles acetate ionic liquid and/
Or quaternary ammonium acetate ionic liquid, it is as catalyst synthesis of propylene glycol.
2. the ionic liquid as claimed in claim 1 application in propylene glycol synthesizes, it is characterised in that described imidazoles acetate ion liquid
Body is at least one in [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC], and described quaternary ammonium acetate ionic liquid is [N2221][AC]、
[N4441] [AC] and [N4444] at least one in [AC].
3. the ionic liquid as claimed in claim 1 or 2 application in propylene glycol synthesizes, it is characterised in that described ionic liquid is
At least one in [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC].
4. a synthetic method for propylene glycol, comprises the steps:
Expoxy propane is sent in reactor with alcohol and contacts with catalyst, be heated to 50 DEG C～200 DEG C under closed environment, it is thus achieved that described propylene glycol,
Wherein, described catalyst is imidazoles acetate ionic liquid and/or quaternary ammonium acetate ionic liquid.
5. the synthetic method of propylene glycol as claimed in claim 4, it is characterised in that described expoxy propane is 1:1～1 with the mol ratio of alcohol:
10, described catalyst is 1:10～1:1000 with the mol ratio of expoxy propane.
6. the synthetic method of propylene glycol as claimed in claim 5, it is characterised in that described expoxy propane is 1:2～1 with the mol ratio of alcohol:
4, described catalyst is 1:50～1:200 with the mol ratio of expoxy propane.
7. the synthetic method of propylene glycol as claimed in claim 4, it is characterised in that the described heat time is 30～300min.
8. the synthetic method of propylene glycol as claimed in claim 4, it is characterised in that described imidazoles acetate ionic liquid be [EMIM] [AC],
At least one in [DMIM] [AC] and [BMIM] [AC], described quaternary ammonium acetate ionic liquid is [N2221][AC]、[N4441] [AC] and
[N4444] at least one in [AC].
9. the synthetic method of the propylene glycol as described in claim 4 or 8, it is characterised in that described ionic liquid be [EMIM] [AC],
At least one in [DMIM] [AC] and [BMIM] [AC].
10. the synthetic method of propylene glycol as claimed in claim 4, it is characterised in that described alcohol is C1～C8Any one in alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610340067.9A CN105921172A (en) | 2016-05-20 | 2016-05-20 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610340067.9A CN105921172A (en) | 2016-05-20 | 2016-05-20 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105921172A true CN105921172A (en) | 2016-09-07 |
Family
ID=56841103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610340067.9A Pending CN105921172A (en) | 2016-05-20 | 2016-05-20 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105921172A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
| CN107096567A (en) * | 2017-05-23 | 2017-08-29 | 中国科学院过程工程研究所 | The composite catalyst and preparation method of synthesis of propylene glycol |
| WO2017197857A1 (en) * | 2016-05-20 | 2017-11-23 | 中国科学院过程工程研究所 | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| CN107661778A (en) * | 2017-09-30 | 2018-02-06 | 辽宁奥克医药辅料股份有限公司 | It is a kind of for the catalyst of oxirane ring-opening reaction and the preparation method of ethoxy compound |
| CN107694602A (en) * | 2017-08-18 | 2018-02-16 | 佳化化学（茂名）有限公司 | A kind of synthetic method of the catalyst for preparing propane diols phenylate and propane diols phenylate |
| CN108212196A (en) * | 2018-01-16 | 2018-06-29 | 中国科学院过程工程研究所 | A kind of preparation method and application of the composite catalyst of synthesis of propylene glycol |
| CN110330459A (en) * | 2019-07-18 | 2019-10-15 | 中国科学院过程工程研究所 | A kind of carboxylate ion liquid and the preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550069A (en) * | 2009-05-25 | 2009-10-07 | 哈尔滨师范大学 | Method for synthesizing propylene glycol methyl ether |
-
2016
- 2016-05-20 CN CN201610340067.9A patent/CN105921172A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550069A (en) * | 2009-05-25 | 2009-10-07 | 哈尔滨师范大学 | Method for synthesizing propylene glycol methyl ether |
Non-Patent Citations (2)
| Title |
|---|
| 张雪红，等: ""嫁接型咪唑类碱性离子液体催化合成丙二醇醚"", 《河北师范大学学报 自然科学版》 * |
| 张雪红，等: ""碱性离子液体官能化SiO2的制备及其催化性能"", 《天然气化工》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017197857A1 (en) * | 2016-05-20 | 2017-11-23 | 中国科学院过程工程研究所 | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| US10604468B2 (en) | 2016-05-20 | 2020-03-31 | Institute Of Process Engineering, Chinese Academy Of Sciences | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
| CN106831358B (en) * | 2017-01-18 | 2020-03-03 | 东营市海科新源化工有限责任公司 | Preparation method of dipropylene glycol |
| CN107096567A (en) * | 2017-05-23 | 2017-08-29 | 中国科学院过程工程研究所 | The composite catalyst and preparation method of synthesis of propylene glycol |
| CN107096567B (en) * | 2017-05-23 | 2019-10-08 | 中国科学院过程工程研究所 | The composite catalyst and preparation method of synthesis of propylene glycol |
| CN107694602A (en) * | 2017-08-18 | 2018-02-16 | 佳化化学（茂名）有限公司 | A kind of synthetic method of the catalyst for preparing propane diols phenylate and propane diols phenylate |
| US11091416B2 (en) | 2017-08-18 | 2021-08-17 | Jiahua Chemicals (Maoming) Co., Ltd. | Catalyst for preparing propylene glycol phenyl ether and method for synthesizing propylene glycol phenyl ether |
| CN107661778A (en) * | 2017-09-30 | 2018-02-06 | 辽宁奥克医药辅料股份有限公司 | It is a kind of for the catalyst of oxirane ring-opening reaction and the preparation method of ethoxy compound |
| CN108212196A (en) * | 2018-01-16 | 2018-06-29 | 中国科学院过程工程研究所 | A kind of preparation method and application of the composite catalyst of synthesis of propylene glycol |
| CN108212196B (en) * | 2018-01-16 | 2020-05-01 | 中国科学院过程工程研究所 | Preparation method and application of composite catalyst for synthesizing propylene glycol ether |
| CN110330459A (en) * | 2019-07-18 | 2019-10-15 | 中国科学院过程工程研究所 | A kind of carboxylate ion liquid and the preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105921172A (en) | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method | |
| CN107400043B (en) | Application of ionic liquid in synthesis of propylene glycol ether and synthesis method of propylene glycol ether | |
| CN106040296B (en) | The preparation method of the poly- propyl ether -3- methylimidazole ionic-liquid catalyst of chlorination 1- amino | |
| CN105688985B (en) | A kind of preparation method of solid-carrying type ionic-liquid catalyst | |
| CN109912544B (en) | Method for preparing bis ((3, 4-epoxycyclohexyl) methyl) adipate by using microchannel reactor | |
| CN108493468A (en) | A kind of epoxy polyphenylene oxide proton membrane and preparation method thereof | |
| CN105642343A (en) | Silicon-supported ionic liquid catalyst | |
| CN105418470A (en) | Synthetic method of clethodim | |
| CN107915644A (en) | A kind of method that p-aminophenyl ether is prepared using paranitrochlorobenzene as raw material | |
| CN110872254B (en) | Pyrazole salt diionic liquid and method for catalytic synthesis of cyclic carbonate by using same | |
| Zhang et al. | Synthesis of carboxylic acids via the hydrocarboxylation of alcohols with CO 2 and H 2 | |
| CN102850223B (en) | Method for synthesizing methylethyl carbonate | |
| CN106925350A (en) | MIL‑101(Cr)‑SO3(m) acidic catalyst | |
| CN104829813B (en) | A kind of ionomeric polymer containing phosphine, preparation method and anion-exchange membrane | |
| CN102295620B (en) | Co-production synthesizing technology of rubber vulcanization promoter NS | |
| CN110885314B (en) | Metal ion liquid, preparation method thereof and application of metal ion liquid in preparation of cyclic carbonate by catalyzing carbon dioxide cycloaddition reaction | |
| CN115028584B (en) | Ionic liquid for producing glutaraldehyde | |
| CN105968364A (en) | Imidazolium salt type poly ionic liquid crosslinking film based on Click reaction and preparation and application of film | |
| Xuewei et al. | Synthesis of a basic imidazolide ionic liquid and its application in catalyzing Knoevenagel condensation | |
| CN102942548B (en) | Delta-dodecalactone synthesis method | |
| CN110078633A (en) | A kind of fluoro- 3- methoxyl group -5- methylaniline hydrochloride preparation method of 4- | |
| CN105622351A (en) | Method for preparing benzenediol | |
| CN104086591B (en) | The preparation method of the phenyl-phosphonic acid trimethoxy silane based on grignard reaction | |
| CN103816937B (en) | The preparation method of the immobilized ionic-liquid catalyst of a kind of urea alcoholysis synthesizing diethyl carbonate | |
| CN103159624B (en) | Method of preparing malonate diester by using malic acid as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160907 |